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Open Chemistry

formerly Central European Journal of Chemistry


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Volume 10, Issue 1

Issues

Volume 13 (2015)

Oxidative addition of methyl iodide to [Rh(PhCOCHCOPh)(CO)(P(OCH2)3CCH3)]: an experimental and computational study

Johannes Erasmus / Jeanet Conradie
Published Online: 2011-11-24 | DOI: https://doi.org/10.2478/s11532-011-0137-0

Abstract

The reaction rate of the oxidative addition and CO insertion steps of methyl iodide with [Rh(PhCOCHCOPh)(CO)(P(OCH2)3CCH3)] are presented. Large negative experimental values for the activation entropy and results from a density functional theory computational chemistry study indicated trans addition of the CH3I to [Rh(PhCOCHCOPh)(CO)(P(OCH2)3CCH3)]. A study of the molecular orbitals gives insight into the flow of electrons during the oxidative addition reaction. CO insertion leads to a square pyramidal [Rh(PhCOCHCOPh)(P(OCH2)3CCH3)(COCH3)(I)] acyl product with the COCH3 moiety in the apical position. The strong electron donation of the P(OCH2)3CCH3 ligand accelerates the oxidation addition step of methyl iodide to [Rh(PhCOCHCOPh)(CO)(P(OCH2)3CCH3)] by ca. 265 times faster (at 35°C) than that of the Monsanto catalyst, but inhibits the CO insertion step.

Keywords: Benzoylacetone; Rhodium; Oxidative addition; Phosphite; DFT

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About the article

Published Online: 2011-11-24

Published in Print: 2012-02-01


Citation Information: Open Chemistry, Volume 10, Issue 1, Pages 256–266, ISSN (Online) 2391-5420, DOI: https://doi.org/10.2478/s11532-011-0137-0.

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© 2011 Versita Warsaw. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License. BY-NC-ND 3.0

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